JP2021161066A - Aqueous polymer emulsion, makeup cosmetic, and method for producing aqueous polymer emulsion - Google Patents
Aqueous polymer emulsion, makeup cosmetic, and method for producing aqueous polymer emulsion Download PDFInfo
- Publication number
- JP2021161066A JP2021161066A JP2020064323A JP2020064323A JP2021161066A JP 2021161066 A JP2021161066 A JP 2021161066A JP 2020064323 A JP2020064323 A JP 2020064323A JP 2020064323 A JP2020064323 A JP 2020064323A JP 2021161066 A JP2021161066 A JP 2021161066A
- Authority
- JP
- Japan
- Prior art keywords
- unsaturated monomer
- ethylenically unsaturated
- polymer
- mass
- aqueous polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 168
- 239000000839 emulsion Substances 0.000 title claims abstract description 105
- 239000002537 cosmetic Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- 239000000178 monomer Substances 0.000 claims abstract description 165
- 239000002245 particle Substances 0.000 claims abstract description 59
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000009477 glass transition Effects 0.000 claims description 20
- -1 m-phenoxybenzyl Chemical group 0.000 claims description 20
- 239000003125 aqueous solvent Substances 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 9
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012528 membrane Substances 0.000 abstract description 7
- 230000008014 freezing Effects 0.000 abstract description 2
- 238000007710 freezing Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- 239000003505 polymerization initiator Substances 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 8
- 230000002209 hydrophobic effect Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- HHQAGBQXOWLTLL-UHFFFAOYSA-N (2-hydroxy-3-phenoxypropyl) prop-2-enoate Chemical compound C=CC(=O)OCC(O)COC1=CC=CC=C1 HHQAGBQXOWLTLL-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 239000004014 plasticizer Substances 0.000 description 6
- BXSPZNVFEYWSLZ-UHFFFAOYSA-N (3-phenoxyphenyl)methyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC(OC=2C=CC=CC=2)=C1 BXSPZNVFEYWSLZ-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 5
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000013049 sediment Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002736 nonionic surfactant Substances 0.000 description 4
- 229920001296 polysiloxane Polymers 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 235000019329 dioctyl sodium sulphosuccinate Nutrition 0.000 description 3
- YHAIUSTWZPMYGG-UHFFFAOYSA-L disodium;2,2-dioctyl-3-sulfobutanedioate Chemical compound [Na+].[Na+].CCCCCCCCC(C([O-])=O)(C(C([O-])=O)S(O)(=O)=O)CCCCCCCC YHAIUSTWZPMYGG-UHFFFAOYSA-L 0.000 description 3
- 201000006747 infectious mononucleosis Diseases 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 102100026735 Coagulation factor VIII Human genes 0.000 description 2
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
- 101000911390 Homo sapiens Coagulation factor VIII Proteins 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- SJIXRGNQPBQWMK-UHFFFAOYSA-N 2-(diethylamino)ethyl 2-methylprop-2-enoate Chemical compound CCN(CC)CCOC(=O)C(C)=C SJIXRGNQPBQWMK-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- DPBJAVGHACCNRL-UHFFFAOYSA-N 2-(dimethylamino)ethyl prop-2-enoate Chemical compound CN(C)CCOC(=O)C=C DPBJAVGHACCNRL-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 1
- QLIBJPGWWSHWBF-UHFFFAOYSA-N 2-aminoethyl methacrylate Chemical compound CC(=C)C(=O)OCCN QLIBJPGWWSHWBF-UHFFFAOYSA-N 0.000 description 1
- UGIJCMNGQCUTPI-UHFFFAOYSA-N 2-aminoethyl prop-2-enoate Chemical compound NCCOC(=O)C=C UGIJCMNGQCUTPI-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- IXPWKHNDQICVPZ-UHFFFAOYSA-N 2-methylhex-1-en-3-yne Chemical compound CCC#CC(C)=C IXPWKHNDQICVPZ-UHFFFAOYSA-N 0.000 description 1
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 1
- JRJNSEMUYTUGLA-UHFFFAOYSA-N 3-phenoxypropyl prop-2-enoate Chemical compound C=CC(=O)OCCCOC1=CC=CC=C1 JRJNSEMUYTUGLA-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- XYVQFUJDGOBPQI-UHFFFAOYSA-N Methyl-2-hydoxyisobutyric acid Chemical compound COC(=O)C(C)(C)O XYVQFUJDGOBPQI-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 239000004909 Moisturizer Substances 0.000 description 1
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- LPQOADBMXVRBNX-UHFFFAOYSA-N ac1ldcw0 Chemical compound Cl.C1CN(C)CCN1C1=C(F)C=C2C(=O)C(C(O)=O)=CN3CCSC1=C32 LPQOADBMXVRBNX-UHFFFAOYSA-N 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- LDHQCZJRKDOVOX-NSCUHMNNSA-N crotonic acid Chemical compound C\C=C\C(O)=O LDHQCZJRKDOVOX-NSCUHMNNSA-N 0.000 description 1
- SPTHWAJJMLCAQF-UHFFFAOYSA-M ctk4f8481 Chemical compound [O-]O.CC(C)C1=CC=CC=C1C(C)C SPTHWAJJMLCAQF-UHFFFAOYSA-M 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000003349 gelling agent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000005397 methacrylic acid ester group Chemical group 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000001333 moisturizer Effects 0.000 description 1
- DNTMQTKDNSEIFO-UHFFFAOYSA-N n-(hydroxymethyl)-2-methylprop-2-enamide Chemical compound CC(=C)C(=O)NCO DNTMQTKDNSEIFO-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L persulfate group Chemical group S(=O)(=O)([O-])OOS(=O)(=O)[O-] JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- VEYCPJGKKJULEP-UHFFFAOYSA-N prop-2-enoic acid sulfuric acid Chemical compound OC(=O)C=C.OS(O)(=O)=O VEYCPJGKKJULEP-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical group CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- 238000010257 thawing Methods 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- 229920001567 vinyl ester resin Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
Abstract
Description
本発明は、水性ポリマーエマルション、メークアップ化粧料及び水性ポリマーエマルションの製造方法に関し、詳しくはメークアップ化粧料に適した水性ポリマーエマルション、この水性ポリマーエマルションを含有するメークアップ化粧料及びこの水性ポリマーエマルションの製造方法に関する。 The present invention relates to an aqueous polymer emulsion, a makeup cosmetic, and a method for producing an aqueous polymer emulsion. Specifically, the present invention relates to an aqueous polymer emulsion suitable for makeup cosmetics, a makeup cosmetic containing the aqueous polymer emulsion, and the aqueous polymer emulsion. Regarding the manufacturing method of.
マニキュアや水性ネイルエナメルなどの爪用化粧料は、爪を装飾することで人に活力や魅力を与える。爪用化粧料の目的の一つとして、爪へのつやの付与が挙げられる。 Nail cosmetics such as nail polish and water-based nail enamel give people vitality and charm by decorating their nails. One of the purposes of nail cosmetics is to give gloss to the nails.
爪用化粧料として、一般にはシリコーン系製剤がよく用いられている。例えば特許文献１には、（メタ）アクリルシリコーン系グラフト共重合体、ニトロセルロース、可塑剤及び非芳香族系溶剤を含有する溶剤系美爪料が開示されている。 Generally, silicone-based preparations are often used as nail cosmetics. For example, Patent Document 1 discloses a solvent-based nail polish containing a (meth) acrylic silicone-based graft copolymer, nitrocellulose, a plasticizer, and a non-aromatic solvent.
しかし、（メタ）アクリルシリコーン系グラフト共重合体などのシリコーン系製剤を用いると、爪用化粧料の密着性が低くなりやすく、爪から爪用化粧料が剥離したり、爪用化粧料の重ね塗りによって爪の上に複数の膜を重ねた場合に膜間の剥離が起こったりしやすくなる。 However, when a silicone-based preparation such as a (meth) acrylic silicone-based graft copolymer is used, the adhesion of the nail cosmetics tends to be low, and the nail cosmetics may peel off from the nails or the nail cosmetics may be layered. When a plurality of films are layered on the nail by application, peeling between the films is likely to occur.
発明者は、溶剤系ではなくメークアップ用途においてよく用いられるＯ／Ｗ型エマルションを爪用化粧料に適用することも検討した。 The inventor also considered applying an O / W emulsion, which is often used in make-up applications, to nail cosmetics rather than solvent-based ones.
しかし、Ｏ／Ｗ型エマルションには、凍結してしまうと、常温に戻しても粒子が凝集したり破壊されたりしてしまうため、再使用不可能となるという問題がある。 However, the O / W type emulsion has a problem that if it is frozen, the particles are aggregated or destroyed even when the temperature is returned to room temperature, so that the emulsion cannot be reused.
この問題に関し、特許文献２には、凍結安定性、凍結復元性の付与のため、スチレン系単量体１５〜３５重量％、アクリル酸系単量体及び／又はメタアクリル酸系単量体６５〜８５重量％及び共重合性単量体０〜４０重量％からなる共重合体又はその塩からなるロジン系サイズ剤用乳化分散剤を用いることが、開示されている。 Regarding this problem, Patent Document 2 describes styrene-based monomer 15 to 35% by weight, acrylic acid-based monomer and / or methacrylic acid-based monomer 65 in order to impart freeze stability and freeze restoration property. It is disclosed to use an emulsion dispersant for a rosin-based sizing agent composed of a copolymer composed of ~ 85% by weight and a copolymerizable monomer 0 to 40% by weight or a salt thereof.
しかし、このような乳化剤は、凍結安定性、凍結復元性の付与のためには多量に使用される必要がある。そのため、特に爪用化粧料に適用される場合には、爪用化粧料から作製される膜のつやなどの特性が悪化しやすい。 However, such an emulsifier needs to be used in a large amount in order to impart freeze stability and freeze stability. Therefore, especially when applied to nail cosmetics, characteristics such as gloss of a film produced from nail cosmetics tend to deteriorate.
本発明の課題は、Ｏ／Ｗ型エマルションを実現でき、凍結してから常温に戻しても流動性が損なわれにくく、かつ膜を作製した場合に膜がつやを有しやすい水性ポリマーエマルション、この水性ポリマーエマルションを含有するメークアップ化粧料及び水性ポリマーエマルションの製造方法を提供することである。 An object of the present invention is an aqueous polymer emulsion that can realize an O / W type emulsion, that does not easily lose its fluidity even when it is frozen and then returned to room temperature, and that the film tends to have a gloss when the film is produced. It is an object of the present invention to provide a make-up cosmetic containing an aqueous polymer emulsion and a method for producing an aqueous polymer emulsion.
本発明の一態様に係る水性ポリマーエマルション（Ｘ）は、ポリマー粒子（Ａ）、高分子乳化剤（Ｂ）、及び水（Ｃ）を含有する。前記ポリマー粒子（Ａ）は、エチレン性不飽和単量体（ａ）の重合体である。前記高分子乳化剤（Ｂ）は、エチレン性不飽和単量体（ｂ）の重合体である。前記エチレン性不飽和単量体（ａ）と前記エチレン性不飽和単量体（ｂ）とのうち少なくとも一方は、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有する。 The aqueous polymer emulsion (X) according to one aspect of the present invention contains polymer particles (A), a polymer emulsifier (B), and water (C). The polymer particles (A) are polymers of the ethylenically unsaturated monomer (a). The polymer emulsifier (B) is a polymer of an ethylenically unsaturated monomer (b). At least one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. ..
本発明の一態様に係るメークアップ化粧料は、前記水性ポリマーエマルション（Ｘ）を含有する。 The make-up cosmetic according to one aspect of the present invention contains the aqueous polymer emulsion (X).
本発明の一態様に係る水性ポリマーエマルション（Ｘ）の製造方法は、ポリマー粒子（Ａ）、高分子乳化剤（Ｂ）、及び水（Ｃ）を含有する水性ポリマーエマルション（Ｘ）の製造方法である。本方法は、水性溶媒中で前記高分子乳化剤（Ｂ）の存在下でエチレン性不飽和単量体（ａ）を乳化重合することで前記ポリマー粒子（Ａ）を合成することを含む。前記高分子乳化剤（Ｂ）は、エチレン性不飽和単量体（ｂ）の重合体である。前記エチレン性不飽和単量体（ａ）と前記エチレン性不飽和単量体（ｂ）とのうち少なくとも一方は、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有する。 The method for producing an aqueous polymer emulsion (X) according to one aspect of the present invention is a method for producing an aqueous polymer emulsion (X) containing polymer particles (A), a polymer emulsifier (B), and water (C). .. The method comprises synthesizing the polymer particles (A) by emulsion polymerization of the ethylenically unsaturated monomer (a) in the presence of the polymer emulsifier (B) in an aqueous solvent. The polymer emulsifier (B) is a polymer of an ethylenically unsaturated monomer (b). At least one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. ..
本発明によると、Ｏ／Ｗ型エマルションを実現でき、凍結してから常温に戻しても流動性が損なわれにくく、かつ膜を作製した場合に膜がつやを有しやすい水性ポリマーエマルション（Ｘ）、この水性ポリマーエマルション（Ｘ）を含有するメークアップ化粧料及び水性ポリマーエマルション（Ｘ）の製造方法を提供できる。 According to the present invention, an O / W type emulsion can be realized, the fluidity is not easily impaired even when the emulsion is frozen and then returned to room temperature, and the film tends to have a gloss when the film is prepared (X). , A make-up cosmetic containing the aqueous polymer emulsion (X) and a method for producing the aqueous polymer emulsion (X) can be provided.
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本実施形態に係る水性ポリマーエマルション（Ｘ）は、ポリマー粒子（Ａ）、高分子乳化剤（Ｂ）、及び水（Ｃ）を含有する。ポリマー粒子（Ａ）は、エチレン性不飽和単量体（ａ）の重合体である。高分子乳化剤（Ｂ）は、エチレン性不飽和単量体（ｂ）の重合体である。エチレン性不飽和単量体（ａ）とエチレン性不飽和単量体（ｂ）とのうち少なくとも一方は、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有する。 The aqueous polymer emulsion (X) according to this embodiment contains polymer particles (A), a polymer emulsifier (B), and water (C). The polymer particles (A) are polymers of the ethylenically unsaturated monomer (a). The polymer emulsifier (B) is a polymer of the ethylenically unsaturated monomer (b). At least one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more.
本実施形態では、ポリマー粒子（Ａ）と高分子乳化剤（Ｂ）とは、ポリマー粒子（Ａ）を高分子乳化剤（Ｂ）が覆うことで、コアシェル構造のエマルション粒子を構成できる。すなわち、エマルション粒子は、コアであるポリマー粒子（Ａ）と、シェルである高分子乳化剤（Ｂ）とを備えている。このため、水性ポリマーエマルション（Ｘ）は、Ｏ／Ｗ型エマルションを実現でき、この水性ポリマーエマルション（Ｘ）中ではエマルション粒子が安定して分散しやすい。また、水性ポリマーエマルション（Ｘ）が凍結してから常温に戻してもエマルション粒子の凝集及び破壊が生じにくい。すなわち、水性ポリマーエマルション（Ｘ）は、良好な凍結復元性を有しやすい。さらに、エチレン性不飽和単量体（ａ）とエチレン性不飽和単量体（ｂ）とのうち少なくとも一方が、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有することで、水性ポリマーエマルション（Ｘ）から作製された膜は良好なつやを有しやすい。 In the present embodiment, the polymer particles (A) and the polymer emulsifier (B) can form emulsion particles having a core-shell structure by covering the polymer particles (A) with the polymer emulsifier (B). That is, the emulsion particles include a polymer particle (A) which is a core and a polymer emulsifier (B) which is a shell. Therefore, the aqueous polymer emulsion (X) can realize an O / W type emulsion, and the emulsion particles are easily dispersed stably in the aqueous polymer emulsion (X). Further, even if the aqueous polymer emulsion (X) is frozen and then returned to room temperature, the emulsion particles are less likely to aggregate and break. That is, the aqueous polymer emulsion (X) tends to have good freeze-restorability. Further, at least one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. As a result, the film prepared from the aqueous polymer emulsion (X) tends to have a good gloss.
本実施形態について、さらに詳しく説明する。 The present embodiment will be described in more detail.
本実施形態において、水性ポリマーエマルション（Ｘ）とは、水（Ｄ）を含有する溶媒と、溶媒中に分散しているエマルション粒子とを含むエマルションをいう。上述のとおり、エマルション粒子は、コアであるポリマー粒子（Ａ）と、シェルである高分子乳化剤（Ｂ）とを備えている。 In the present embodiment, the aqueous polymer emulsion (X) refers to an emulsion containing a solvent containing water (D) and emulsion particles dispersed in the solvent. As described above, the emulsion particles include a polymer particle (A) which is a core and a polymer emulsifier (B) which is a shell.
上述のとおり、ポリマー粒子（Ａ）はエチレン性不飽和単量体（ａ）の重合体、高分子乳化剤（Ｂ）はエチレン性不飽和単量体（ｂ）の重合体であり、かつエチレン性不飽和単量体（ａ）とエチレン性不飽和単量体（ｂ）とのうち少なくとも一方は、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有する。すなわち、エチレン性不飽和単量体（ａ）とエチレン性不飽和単量体（ｂ）とのうち一方のみがエチレン性不飽和単量体（ｃ）を含有してもよく、両方がエチレン性不飽和単量体（ｃ）を含有してもよい。言い換えると、ポリマー粒子（Ａ）と高分子乳化剤（Ｂ）とのうち一方のみがエチレン性不飽和単量体（ｃ）に由来する構成単位を有してもよく、両方がエチレン性不飽和単量体（ｃ）に由来する構成単位を有してもよい。 As described above, the polymer particles (A) are a polymer of an ethylenically unsaturated monomer (a), and the polymer emulsifier (B) is a polymer of an ethylenically unsaturated monomer (b), and are ethylenic. At least one of the unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains the ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. That is, only one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) may contain the ethylenically unsaturated monomer (c), and both are ethylenic. It may contain an unsaturated monomer (c). In other words, only one of the polymer particles (A) and the polymer emulsifier (B) may have a structural unit derived from the ethylenically unsaturated monomer (c), and both may have ethylenically unsaturated monomers. It may have a structural unit derived from the polymer (c).
エチレン性不飽和単量体（ｃ）の屈折率とは、例えば２５℃のエチレン性不飽和単量体（ｃ）にＮａのＤ線（５８９．３ｎｍ）を照射して測定される値でありうる。 The refractive index of the ethylenically unsaturated monomer (c) is, for example, a value measured by irradiating the ethylenically unsaturated monomer (c) at 25 ° C. with the D line (589.3 nm) of Na. sell.
エチレン性不飽和単量体（ｃ）は、芳香環を有する単量体を含有することが好ましい。この場合、水性ポリマーエマルション（Ｘ）から作製される膜は耐水性を有しやすく、そのため汗、水などに晒された場合の膜の耐久性が高くなりやすい。また芳香環を有する単量体は屈折率が高く、膜の良好なつや感を得ることができる。芳香環を有する単量体は、例えばスチレン、α−メチルスチレン、クロロスチレン、アルキルスチレン、及びジビニルベンゼン等の芳香族モノ及びジビニル化合物；並びにｍ−フェノキシベンジルアクリレート（ｍＰＢＡ）及び２−ヒドロキシ−３−フェノキシプロピルアクリレート（ＨＰＰＡ）等の芳香環を有する（メタ）アクリル系単量体からなる群から選択される少なくとも一種を含有する。 The ethylenically unsaturated monomer (c) preferably contains a monomer having an aromatic ring. In this case, the film made from the aqueous polymer emulsion (X) tends to have water resistance, and therefore the durability of the film when exposed to sweat, water, or the like tends to increase. Further, the monomer having an aromatic ring has a high refractive index, and a good glossy feeling of the film can be obtained. Aromatic monomers include aromatic mono and divinyl compounds such as styrene, α-methylstyrene, chlorostyrene, alkylstyrene, and divinylbenzene; and m-phenoxybenzyl acrylate (mPBA) and 2-hydroxy-3. -Contains at least one selected from the group consisting of (meth) acrylic monomers having an aromatic ring such as phenoxypropyl acrylate (HPPA).
エチレン性不飽和単量体（ｃ）は、芳香環を有する（メタ）アクリル系単量体を含有することが好ましい。この場合、エチレン性不飽和単量体（ｃ）は、エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々を構成する他の（メタ）アクリル系単量体との共重合性が良く、かつ膜のガラス転移温度の過度な上昇を引き起こしにくい。そのため、膜が形成されやすく、かつ膜が脆くなりにくい。エチレン性不飽和単量体（ｃ）がｍ−フェノキシベンジルアクリレート（ｍＰＢＡ）及び２−ヒドロキシ−３−フェノキシプロピルアクリレート（ＨＰＰＡ）のうち、少なくとも一方を含有すれば、より好ましい。エチレン性不飽和単量体（ｃ）は、芳香族モノビニル化合物、芳香族ジビニル化合物などの、芳香族ビニル化合物を含有しないことが好ましい。この場合、膜がより形成されやすく、かつ膜がより脆くなりにくい。ただし、本実施形態の効果を過度に損なわない範囲内でエチレン性不飽和単量体（ｃ）が芳香族ビニル化合物を含有してもよい。 The ethylenically unsaturated monomer (c) preferably contains a (meth) acrylic monomer having an aromatic ring. In this case, the ethylenically unsaturated monomer (c) is another (meth) acrylic-based single amount constituting each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b). It has good copolymerizability with the body and is unlikely to cause an excessive increase in the glass transition temperature of the film. Therefore, the film is easily formed and the film is less likely to become brittle. It is more preferable that the ethylenically unsaturated monomer (c) contains at least one of m-phenoxybenzyl acrylate (mPBA) and 2-hydroxy-3-phenoxypropyl acrylate (HPPA). The ethylenically unsaturated monomer (c) preferably does not contain an aromatic vinyl compound such as an aromatic monovinyl compound or an aromatic divinyl compound. In this case, the film is more likely to be formed and the film is less likely to be brittle. However, the ethylenically unsaturated monomer (c) may contain an aromatic vinyl compound within a range that does not excessively impair the effects of the present embodiment.
エチレン性不飽和単量体（ａ）がエチレン性不飽和単量体（ｃ）を含有する場合、エチレン性不飽和単量体（ａ）に対する、エチレン性不飽和単量体（ａ）中のエチレン性不飽和単量体（ｃ）の割合は、１質量％以上８０質量％以下であることが好ましい。この割合が１質量％以上であると、膜のつやが特に良好になりやすい。また、この割合が８０質量％以下であると、水性ポリマーエマルション（Ｘ）が安定したＯ／Ｗ型エマルションを特に実現しやすい。この割合は、５質量％以上７０質量％以下であればより好ましく、１０質量％以上６０質量％以下であれば更に好ましい。 When the ethylenically unsaturated monomer (a) contains the ethylenically unsaturated monomer (c), the ethylenically unsaturated monomer (a) is contained in the ethylenically unsaturated monomer (a) with respect to the ethylenically unsaturated monomer (a). The proportion of the ethylenically unsaturated monomer (c) is preferably 1% by mass or more and 80% by mass or less. When this ratio is 1% by mass or more, the gloss of the film tends to be particularly good. Further, when this ratio is 80% by mass or less, it is particularly easy to realize an O / W type emulsion in which the aqueous polymer emulsion (X) is stable. This ratio is more preferably 5% by mass or more and 70% by mass or less, and further preferably 10% by mass or more and 60% by mass or less.
エチレン性不飽和単量体（ｂ）がエチレン性不飽和単量体（ｃ）を含有する場合、エチレン性不飽和単量体（ｂ）に対する、エチレン性不飽和単量体（ｂ）中のエチレン性不飽和単量体（ｃ）の割合は、１質量％以上８０質量％以下であることが好ましい。この割合が１質量％以上であると、膜のつやが特に良好になりやすい。また、この割合が８０質量％以下であると、水性ポリマーエマルション（Ｘ）が安定したＯ／Ｗ型エマルションを特に実現しやすい。この割合は、５質量％以上７０質量％以下であればより好ましく、１０質量％以上６０質量％以下であれば更に好ましい。 When the ethylenically unsaturated monomer (b) contains the ethylenically unsaturated monomer (c), it is contained in the ethylenically unsaturated monomer (b) with respect to the ethylenically unsaturated monomer (b). The proportion of the ethylenically unsaturated monomer (c) is preferably 1% by mass or more and 80% by mass or less. When this ratio is 1% by mass or more, the gloss of the film tends to be particularly good. Further, when this ratio is 80% by mass or less, it is particularly easy to realize an O / W type emulsion in which the aqueous polymer emulsion (X) is stable. This ratio is more preferably 5% by mass or more and 70% by mass or less, and further preferably 10% by mass or more and 60% by mass or less.
またエチレン性不飽和単量体（ｃ）の割合が水性ポリマーエマルション（Ｘ）の固形分に対して１質量％以上８０質量％以下であれば、膜のつやがより良好になりやすい。この割合は５質量％以上７０質量％以下であればより好ましく、１０質量％以上６０質量％以下であれば更に好ましい。 Further, when the proportion of the ethylenically unsaturated monomer (c) is 1% by mass or more and 80% by mass or less with respect to the solid content of the aqueous polymer emulsion (X), the gloss of the film tends to be better. This ratio is more preferably 5% by mass or more and 70% by mass or less, and further preferably 10% by mass or more and 60% by mass or less.
エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々は、エチレン性不飽和単量体（ｃ）以外に、適宜の単量体を含有でき、親水性単量体と疎水性単量体とのうちいずれも含有できる。 Each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) can contain an appropriate monomer in addition to the ethylenically unsaturated monomer (c), and is hydrophilic. Both the metric and the hydrophobic monomer can be contained.
エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々が親水性単量体を含有する場合、親水性単量体は、例えばアクリル酸、メタクリル酸、イタコン酸、マレイン酸、フマル酸、及びクロトン酸等のエチレン性不飽和カルボン酸；ヒドロキシエチルアクリレート、ヒドロキシエチルメタクリレート、グリシジルアクリレート、グリシジルメタクリレート、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、ポリエチレングリコールモノアクリレート、及びポリエチレングリコールモノメタクリレート等のヒドロキシ基又はグリシジル基含有エチレン性単量体；並びにアクリルアミド、メタクリルアミド、Ｎ−メチロールアクリルアミド、Ｎ−メチロールメタクリルアミド、及びＮ−ダイアセトンアクリルアミド等のエチレン性アミド；アミノエチルアクリレート、アミノエチルメタクリレート、Ｎ，Ｎ−ジメチルアミノエチルアクリレート、Ｎ，Ｎ−ジメチルアミノエチルメタクリレート、Ｎ，Ｎ−ジエチルアミノエチルアクリレート、Ｎ，Ｎ−ジエチルアミノエチルメタクリレート、Ｎ，Ｎ，Ｎ−トリメチルアミノエチルアクリレート、及びＮ，Ｎ，Ｎ−トリメチルアミノエチルメタクリレート等のエチレン性アミン及びその塩等からなる群から選択される少なくとも一種の単量体を含有する。 When each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains a hydrophilic monomer, the hydrophilic monomer is, for example, acrylic acid, methacrylic acid, or itaconic acid. , Maleic acid, fumaric acid, and ethylenically unsaturated carboxylic acids such as crotonic acid; hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, polyethylene glycol monoacrylate, and polyethylene. Hydroxy or glycidyl group-containing ethylenic monomers such as glycol monomethacrylate; and ethylenic amides such as acrylamide, methacrylicamide, N-methylolacrylamide, N-methylolmethacrylicamide, and N-diacetoneacrylamide; aminoethylacrylate, Aminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N, N-trimethylaminoethyl acrylate, and It contains at least one monomer selected from the group consisting of ethylenic amines such as N, N, N-trimethylaminoethyl methacrylate and salts thereof.
エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々が疎水性単量体を含有する場合、疎水性単量体は、例えばスチレン、α−メチルスチレン、クロロスチレン、アルキルスチレン、及びジビニルベンゼン等の芳香族モノ及びジビニル化合物；ｍ−フェノキシベンジルアクリレート（ｍＰＢＡ）及び２−ヒドロキシ−３−フェノキシプロピルアクリレート（ＨＰＰＡ）等の芳香環を有する（メタ）アクリル系単量体；メチルアクリレート、メチルメタクリレート、エチルアクリレート、エチルメタクリレート、プロピルアクリレート、プロピルメタクリレート、ブチルアクリレート、ブチルメタクリレート、２−エチルヘキシルアクリレート、２−エチルヘキシルメタクリレート、ターシャリーブチルアクリレート、及びターシャリーブチルメタクリレート等のアクリル酸エステル及びメタクリル酸エステル；アクリロニトリル、及びメタクリロニトリル等のシアン化ビニル化合物；酢酸ビニル等のビニルエステル；並びに塩化ビニル、塩化ビニリデン等のハロゲン化ビニル等からなる群から選択される少なくとも一種の単量体を含有する。なお、このように、上記のエチレン性不飽和単量体（ｃ）に含まれる芳香族モノ及びジビニル化合物及び芳香環を有する（メタ）アクリル系単量体は、疎水性単量体に含まれる。 When each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains a hydrophobic monomer, the hydrophobic monomer is, for example, styrene, α-methylstyrene, or chloro. Aromatic monomers and divinyl compounds such as styrene, alkylstyrene, and divinylbenzene; (meth) acrylic monos having aromatic rings such as m-phenoxybenzyl acrylate (mPBA) and 2-hydroxy-3-phenoxypropyl acrylate (HPPA). Quantities: Acrylate such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, tertiary butyl acrylate, and tertiary butyl methacrylate. At least one selected from the group consisting of acid esters and methacrylic acid esters; vinyl cyanide compounds such as acrylonitrile and methacrylnitrile; vinyl esters such as vinyl acetate; and vinyl halides such as vinyl chloride and vinylidene chloride. Contains a weight. As described above, the aromatic mono and divinyl compounds contained in the ethylenically unsaturated monomer (c) and the (meth) acrylic monomer having an aromatic ring are contained in the hydrophobic monomer. ..
エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々は、（メタ）アクリル系単量体を含有することが好ましい。また、エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々は、スチレン系単量体などの芳香族ビニル化合物を含有しないことが好ましい。この場合、エチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々を構成する（メタ）アクリル系単量体との共重合性が良く、かつ膜のガラス転移温度の過度な上昇を引き起こしにくいので、膜が形成されやすく、かつ膜が脆くなりにくい。ただし、本実施形態の効果を過度に損なわない範囲内でエチレン性不飽和単量体（ａ）及びエチレン性不飽和単量体（ｂ）の各々が芳香族ビニル化合物を含有してもよい。 Each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) preferably contains a (meth) acrylic monomer. Further, it is preferable that each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) does not contain an aromatic vinyl compound such as a styrene-based monomer. In this case, the copolymerizability with the (meth) acrylic monomer constituting each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) is good, and the glass transition of the film is good. Since it is unlikely to cause an excessive rise in temperature, the film is likely to be formed and the film is less likely to become brittle. However, each of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) may contain an aromatic vinyl compound within a range that does not excessively impair the effects of the present embodiment.
エチレン性不飽和単量体（ａ）中の、親水性単量体の含有割合は０質量％以上３０質量％以下であり、疎水性単量体の含有割合は７０質量％以上１００質量％以下であることが好ましい。この場合、高分子乳化剤（Ｂ）を用いた乳化重合によりポリマー粒子（Ａ）が特に安定して合成されやすく、かつエマルション粒子が特に安定して分散しやすい。親水性単量体の含有割合が０質量％以上１５質量％以下であり、疎水性単量体の含有割合は８５質量％以上１００質量％以下であれば、より好ましい。 The content ratio of the hydrophilic monomer in the ethylenically unsaturated monomer (a) is 0% by mass or more and 30% by mass or less, and the content ratio of the hydrophobic monomer is 70% by mass or more and 100% by mass or less. Is preferable. In this case, the polymer particles (A) are particularly stable and easily synthesized by emulsion polymerization using the polymer emulsifier (B), and the emulsion particles are particularly stable and easily dispersed. It is more preferable that the content ratio of the hydrophilic monomer is 0% by mass or more and 15% by mass or less, and the content ratio of the hydrophobic monomer is 85% by mass or more and 100% by mass or less.
エチレン性不飽和単量体（ｂ）中の、親水性単量体の含有割合は５質量％以上４０質量％以下であり、疎水性単量体の含有割合は６０質量％以上９５質量％以下であることが好ましい。この場合、高分子乳化剤（Ｂ）を用いた乳化重合によりポリマー粒子（Ａ）が特に安定して合成されやすく、かつエマルション粒子が特に安定して分散しやすい。親水性単量体の含有割合が１０質量％以上３５質量％以下であり、疎水性単量体の含有割合は６５質量％以上９０質量％以下であれば、より好ましい。 The content ratio of the hydrophilic monomer in the ethylenically unsaturated monomer (b) is 5% by mass or more and 40% by mass or less, and the content ratio of the hydrophobic monomer is 60% by mass or more and 95% by mass or less. Is preferable. In this case, the polymer particles (A) are particularly stable and easily synthesized by emulsion polymerization using the polymer emulsifier (B), and the emulsion particles are particularly stable and easily dispersed. It is more preferable that the content ratio of the hydrophilic monomer is 10% by mass or more and 35% by mass or less, and the content ratio of the hydrophobic monomer is 65% by mass or more and 90% by mass or less.
エチレン性不飽和単量体（ｂ）は、特にアニオン性のエチレン性不飽和単量体を含有することが好ましい。すなわち、高分子乳化剤（Ｂ）はアニオン性であることが好ましい。この場合、高分子乳化剤（Ｂ）を用いた乳化重合によりポリマー粒子（Ａ）が安定して合成されやすく、かつポリマー粒子（Ａ）と高分子乳化剤（Ｂ）とを備えるエマルション粒子が安定して分散しやすい。アニオン性のエチレン性不飽和単量体は、例えば（メタ）アクリル酸等を含有する。 The ethylenically unsaturated monomer (b) preferably contains an anionic ethylenically unsaturated monomer. That is, the polymer emulsifier (B) is preferably anionic. In this case, the polymer particles (A) can be stably synthesized by emulsion polymerization using the polymer emulsifier (B), and the emulsion particles containing the polymer particles (A) and the polymer emulsifier (B) can be stably synthesized. Easy to disperse. The anionic ethylenically unsaturated monomer contains, for example, (meth) acrylic acid.
高分子乳化剤（Ｂ）の酸価が７０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下であることも好ましい。すなわち、高分子乳化剤（Ｂ）の酸価が７０ｍｇＫＯＨ／ｇ以上２５０ｍｇＫＯＨ／ｇ以下であるように、エチレン性不飽和単量体（ｂ）中のアニオン性のエチレン性不飽和単量体の割合が規定されていることが好ましい。この場合、高分子乳化剤（Ｂ）を用いた乳化重合によりポリマー粒子（Ａ）が特に安定して合成されやすく、かつ水性ポリマーエマルション（Ｘ）中でエマルション粒子が特に安定して分散しやすい。高分子乳化剤（Ｂ）の酸価は、１００ｍｇＫＯＨ／ｇ以上２３０ｍｇＫＯＨ／ｇ以下であればより好ましく、１４０ｍｇＫＯＨ／ｇ以上２１０ｍｇＫＯＨ／ｇ以下であれば更に好ましい。 It is also preferable that the acid value of the polymer emulsifier (B) is 70 mgKOH / g or more and 250 mgKOH / g or less. That is, the proportion of the anionic ethylenically unsaturated monomer in the ethylenically unsaturated monomer (b) is such that the acid value of the polymer emulsifier (B) is 70 mgKOH / g or more and 250 mgKOH / g or less. It is preferable that it is specified. In this case, the polymer particles (A) are particularly stable and easily synthesized by emulsion polymerization using the polymer emulsifier (B), and the emulsion particles are particularly easily dispersed in the aqueous polymer emulsion (X). The acid value of the polymer emulsifier (B) is more preferably 100 mgKOH / g or more and 230 mgKOH / g or less, and further preferably 140 mgKOH / g or more and 210 mgKOH / g or less.
エチレン性不飽和単量体（ｂ）が、炭素数８以上１８以下のアルキル基を有する（メタ）アクリル酸エステル（ｂ２）を含有することも好ましい。この場合、水性ポリマーエマルション（Ｘ）が凍結安定性を有しやすい。（メタ）アクリル酸エステル（ｂ２）の割合は、エチレン性不飽和単量体（ｂ）に対して５質量％以上６０質量％以下であることが好ましい。この場合、水性ポリマーエマルション（Ｘ）が凍結安定性を有しつつ、安定的にポリマー粒子（Ａ）が合成されやすい。この割合は１０質量％以上４０質量％以下であればより好ましく、１５質量％以上３０質量％以下であれば更に好ましい。 It is also preferable that the ethylenically unsaturated monomer (b) contains a (meth) acrylic acid ester (b2) having an alkyl group having 8 or more and 18 or less carbon atoms. In this case, the aqueous polymer emulsion (X) tends to have freeze stability. The ratio of the (meth) acrylic acid ester (b2) is preferably 5% by mass or more and 60% by mass or less with respect to the ethylenically unsaturated monomer (b). In this case, the aqueous polymer emulsion (X) has freeze stability, and the polymer particles (A) can be easily synthesized stably. This ratio is more preferably 10% by mass or more and 40% by mass or less, and further preferably 15% by mass or more and 30% by mass or less.
高分子乳化剤（Ｂ）のガラス転移温度は、−５０℃以上１００℃以下であることが好ましい。この場合、水性ポリマーエマルション（Ｘ）から作製される膜のガラス転移温度の過度な上昇を引き起こしにくいので、膜が形成されやすく、かつ膜が脆くなりにくい。このガラス転移温度は、３０℃以上７０℃以下であればより好ましい。 The glass transition temperature of the polymer emulsifier (B) is preferably −50 ° C. or higher and 100 ° C. or lower. In this case, since it is difficult to cause an excessive increase in the glass transition temperature of the film produced from the aqueous polymer emulsion (X), the film is likely to be formed and the film is unlikely to become brittle. The glass transition temperature is more preferably 30 ° C. or higher and 70 ° C. or lower.
高分子乳化剤（Ｂ）の重量平均分子量は６０００以上２００００以下であることが好ましい。この場合、ポリマー粒子（Ａ）を安定的に合成しやすく、かつエマルション粒子が安定して分散しやすい。この重量平均分子量は、８０００以上１５０００以下であればより好ましい。なお、高分子乳化剤（Ｂ）の重量平均分子量は、サイズ排除クロマトグラフィー（ポリスチレン換算）により測定される。 The weight average molecular weight of the polymer emulsifier (B) is preferably 6000 or more and 20000 or less. In this case, the polymer particles (A) are easily synthesized stably, and the emulsion particles are easily dispersed stably. The weight average molecular weight is more preferably 8000 or more and 15000 or less. The weight average molecular weight of the polymer emulsifier (B) is measured by size exclusion chromatography (in terms of polystyrene).
なお、高分子乳化剤（Ｂ）は、市販品から選択されてもよい。 The polymer emulsifier (B) may be selected from commercially available products.
エチレン性不飽和単量体（ａ）に対する高分子乳化剤（Ｂ）の割合は、１５質量％以上６０質量％以下であることが好ましい。この場合、高分子乳化剤（Ｂ）を用いた乳化重合により、水性ポリマーエマルション（Ｘ）が凍結安定性を有しつつ、ポリマー粒子（Ａ）が特に安定して合成されやすく、かつエマルション粒子が特に安定して分散しやすい。この割合は、２０質量％以上５０質量％以下であればより好ましく、２５質量％以上４０質量％以下であれば更に好ましい。 The ratio of the polymer emulsifier (B) to the ethylenically unsaturated monomer (a) is preferably 15% by mass or more and 60% by mass or less. In this case, by emulsion polymerization using the polymer emulsifier (B), the aqueous polymer emulsion (X) has freeze stability, the polymer particles (A) are particularly stable and easily synthesized, and the emulsion particles are particularly stable. Stable and easy to disperse. This ratio is more preferably 20% by mass or more and 50% by mass or less, and further preferably 25% by mass or more and 40% by mass or less.
ポリマー粒子（Ａ）の重量平均分子量は３０００００以下であることが好ましく、１５００００以上２５００００以下であれば更に好ましい。この場合、水性ポリマーエマルション（Ｘ）から作成される膜は丈夫かつ耐水性を有しやすい。この場合のポリマー粒子（Ａ）の重量平均分子量は、１５００００以上２２００００以下であればより好ましい。なお、ポリマー粒子（Ａ）の重量平均分子量は、サイズ排除クロマトグラフィー（ポリスチレン換算）により測定される。 The weight average molecular weight of the polymer particles (A) is preferably 300,000 or less, and more preferably 150,000 or more and 250,000 or less. In this case, the film made from the aqueous polymer emulsion (X) tends to be strong and water resistant. In this case, the weight average molecular weight of the polymer particles (A) is more preferably 150,000 or more and 220,000 or less. The weight average molecular weight of the polymer particles (A) is measured by size exclusion chromatography (in terms of polystyrene).
ポリマー粒子（Ａ）のガラス転移温度は、１０℃以上６０℃以下であるであることが好ましい。この場合、水性ポリマーエマルション（Ｘ）から作製される膜のガラス転移温度の過度な上昇を引き起こしにくいので、膜が形成されやすく、かつ膜が脆くなりにくい。このガラス転移温度は、１５℃以上４０℃以下であればより好ましい。 The glass transition temperature of the polymer particles (A) is preferably 10 ° C. or higher and 60 ° C. or lower. In this case, since it is difficult to cause an excessive increase in the glass transition temperature of the film produced from the aqueous polymer emulsion (X), the film is likely to be formed and the film is unlikely to become brittle. The glass transition temperature is more preferably 15 ° C. or higher and 40 ° C. or lower.
コアであるポリマー粒子（Ａ）とシェルである高分子乳化剤（Ｂ）とを備えるエマルション粒子のガラス転移温度は、１０℃以上５０℃以下であることが好ましい。この場合、水性ポリマーエマルション（Ｘ）から作製される膜のガラス転移温度の過度な上昇を引き起こしにくいので、膜が形成されやすく、かつ膜が脆くなりにくく、べたつきを生じない。このガラス転移温度は、１５℃以上３５℃以下であればより好ましい。 The glass transition temperature of the emulsion particles containing the polymer particles (A) as the core and the polymer emulsifier (B) as the shell is preferably 10 ° C. or higher and 50 ° C. or lower. In this case, since the glass transition temperature of the film produced from the aqueous polymer emulsion (X) is unlikely to rise excessively, the film is likely to be formed, the film is less likely to become brittle, and stickiness does not occur. The glass transition temperature is more preferably 15 ° C. or higher and 35 ° C. or lower.
水性ポリマーエマルション（Ｘ）は水性溶媒を含有し、水性溶媒は水（Ｄ）を含有する。すなわち、水性ポリマーエマルション（Ｘ）は水（Ｄ）を含有する。水性溶媒は水（Ｄ）のみを含有してもよく、水（Ｄ）と親水性有機溶媒とを含有してもよい。親水性有機溶媒とは、水と容易に混和する、あるいは水に容易に溶解する有機溶媒である。親水性有機溶媒は、例えばメタノール、エタノール、プロピルアルコール、イソプロピルアルコール、プロピレングリコールモノメチルエーテル、エチレングリコール、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノターシャリーブチルエーテル、ポリエチレングリコールモノメチルエーテル、及び２−ヒドロキシイソ酪酸メチルからなる群から選択される少なくとも一種の成分を含有できる。 The aqueous polymer emulsion (X) contains an aqueous solvent, and the aqueous solvent contains water (D). That is, the aqueous polymer emulsion (X) contains water (D). The aqueous solvent may contain only water (D), or may contain water (D) and a hydrophilic organic solvent. The hydrophilic organic solvent is an organic solvent that is easily miscible with water or easily dissolved in water. Hydrophilic organic solvents include, for example, methanol, ethanol, propyl alcohol, isopropyl alcohol, propylene glycol monomethyl ether, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoternary butyl ether, polyethylene glycol monomethyl ether, and 2. -Can contain at least one component selected from the group consisting of methyl hydroxyisobutyrate.
水性ポリマーエマルション（Ｘ）の製造方法について説明する。 A method for producing the aqueous polymer emulsion (X) will be described.
水性ポリマーエマルション（Ｘ）の製造方法は、水性溶媒中で、高分子乳化剤（Ｂ）の存在下でエチレン性不飽和単量体（ａ）を乳化重合することでポリマー粒子（Ａ）を合成することを含む。 The method for producing the aqueous polymer emulsion (X) is to synthesize the polymer particles (A) by emulsion polymerization of the ethylenically unsaturated monomer (a) in the presence of the polymer emulsifier (B) in an aqueous solvent. Including that.
水性溶媒は、水（Ｄ）を含有する。水性溶媒は、水（Ｄ）のみを含有してもよく、水（Ｄ）と親水性有機溶媒とを含有してもよい。親水性有機溶媒については既に説明したとおりである。 The aqueous solvent contains water (D). The aqueous solvent may contain only water (D), or may contain water (D) and a hydrophilic organic solvent. The hydrophilic organic solvent has already been described.
エチレン性不飽和単量体（ａ）を乳化重合させる際には、分散安定化のために、高分子乳化剤（Ｂ）以外の界面活性剤を使用してもよい。界面活性剤には特に制限はなく、一般のアニオン系、カチオン系及びノニオン系界面活性剤、エチレン性不飽和結合をもつ反応性活性剤からなる群から選択される少なくとも一種を使用できる。アニオン系界面活性剤とノニオン系界面活性剤との組合せ、カチオン系界面活性剤とノニオン系界面活性剤の組合せ等のように、二種以上の界面活性剤を併用してもよい。ノニオン系界面活性剤は、例えばポリエチレンオキサイドアルキルエーテル、ポリエチレンオキサイドアルキルフェニルエーテル、及びポリエチレンオキサイド−ポリプロピレンオキサイドブロックコポリマー等からなる群から選択される少なくとも一種を含有できる。アニオン系界面活性剤は、例えばアルキルベンゼンスルホネート、アルキルナフタレン−スルホネート、及びポリエチレンオキサイドアルキルエーテルサルフェート等からなる群から選択される少なくとも一種を含有できる。 When the ethylenically unsaturated monomer (a) is emulsion-polymerized, a surfactant other than the polymer emulsifier (B) may be used for dispersion stabilization. The surfactant is not particularly limited, and at least one selected from the group consisting of general anionic, cationic and nonionic surfactants, and reactive active agents having an ethylenically unsaturated bond can be used. Two or more kinds of surfactants may be used in combination, such as a combination of an anionic surfactant and a nonionic surfactant, a combination of a cationic surfactant and a nonionic surfactant, and the like. The nonionic surfactant can contain at least one selected from the group consisting of, for example, polyethylene oxide alkyl ether, polyethylene oxide alkyl phenyl ether, polyethylene oxide-polypropylene oxide block copolymer and the like. The anionic surfactant can contain at least one selected from the group consisting of, for example, alkylbenzene sulfonate, alkylnaphthalene-sulfonate, polyethylene oxide alkyl ether sulfate and the like.
カチオン系界面活性剤は、例えば脂肪族炭化水素基を有する第１級アミン塩、第２級アミン塩、第３級アミン塩、及び第４級アンモニウム塩等からなる群から選択される少なくとも一種を含有できる。 The cationic surfactant is at least one selected from the group consisting of, for example, a primary amine salt having an aliphatic hydrocarbon group, a secondary amine salt, a tertiary amine salt, a quaternary ammonium salt, and the like. Can be contained.
エチレン性不飽和結合を持つ反応性活性剤は、アニオン系とノニオン系のどちらでもよく、例えばアルキルエーテル系、スルホコハク酸エステル系、アルキルフェニルエーテル系、アルキルフェニルエステル系、（メタ）アクリレート硫酸エステル系、リン酸エステル系からなる群から選択される少なくとも一種を含有できる。 The reactive activator having an ethylenically unsaturated bond may be either an anionic type or a nonionic type, for example, an alkyl ether type, a sulfosuccinic acid ester type, an alkylphenyl ether type, an alkylphenyl ester type, or a (meth) acrylate sulfate type. , At least one selected from the group consisting of phosphate esters can be contained.
界面活性剤の量は、エチレン性不飽和単量体（ａ）１００質量部に対して、５質量部以下が好ましく、３質量部以下がさらに好ましい。この場合、膜の物性及び密着性が劣化しにくい。 The amount of the surfactant is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, based on 100 parts by mass of the ethylenically unsaturated monomer (a). In this case, the physical characteristics and adhesion of the film are unlikely to deteriorate.
重合開始剤の存在下でエチレン性不飽和単量体（ａ）を乳化重合させることも好ましい。重合開始剤は、例えば有機系重合開始剤と無機系重合開始剤とのうち少なくとも一方を含有する。有機系重合開始剤は、例えばクメンハイドロパーオキサイド、ジイソプロピルベンゼンハイドロパーオキサイド、及びパラメンタンハイドロパーオキサイドなどのハイドロパーオキサイド類；ベンゾイルパーオキサイド、及びラウロイルパーオキサイド等のパーオキサイド類；並びにアゾビスイソブチロニトリル等のアゾ化合物類等からなる群から選択される少なくとも一種を含有する。無機系重合開始剤は、例えば過硫酸カリウム、過硫酸ナトリウム、及び過硫酸アンモニウムなどの過硫酸塩からなる群から選択される少なくとも一種を含有する。重合開始剤は、更に重亜硫酸ナトリウム、アスコルビン酸及びその塩等の還元剤を含有してもよい。有機系重合開始剤と無機系重合開始剤とのうち少なくとも一方と、還元剤との組み合わせにより、レドックス系重合開始剤が構成される。なお、重合開始剤は前記のみには制限されない。 It is also preferable to emulsion-polymerize the ethylenically unsaturated monomer (a) in the presence of a polymerization initiator. The polymerization initiator contains, for example, at least one of an organic polymerization initiator and an inorganic polymerization initiator. Organic polymerization initiators include, for example, hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, and paramentan hydroperoxide; peroxides such as benzoyl peroxide and lauroyl peroxide; and azobisisobuty. It contains at least one selected from the group consisting of azo compounds such as butyronitrile. The inorganic polymerization initiator contains at least one selected from the group consisting of persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, for example. The polymerization initiator may further contain a reducing agent such as sodium bisulfite, ascorbic acid and a salt thereof. A redox-based polymerization initiator is composed of a combination of at least one of the organic-based polymerization initiator and the inorganic-based polymerization initiator and a reducing agent. The polymerization initiator is not limited to the above.
水性ポリマーエマルション（Ｘ）を製造する際には、例えばまず必要に応じて水性溶媒中に、エチレン性不飽和単量体（ａ）を中和するための中和剤を加える。中和剤は例えばアンモニア水である。続いて水性溶媒を必要により加熱しながら、水性溶媒に高分子乳化剤（Ｂ）を加える。続いて、不活性雰囲気下で、水性溶媒を加熱しながら、水性溶媒中に重合開始剤とエチレン性不飽和単量体（ａ）とを加える。これにより、水性溶媒中でエチレン性不飽和単量体（ａ）を乳化重合させて、ポリマー粒子（Ａ）を合成する。これにより、水性ポリマーエマルション（Ｘ）が得られる。エチレン性不飽和単量体（ａ）を乳化重合させるための反応条件は、高分子乳化剤（Ｂ）の組成、エチレン性不飽和単量体（ａ）の組成などに応じて、適宜設定される。 When producing the aqueous polymer emulsion (X), for example, a neutralizing agent for neutralizing the ethylenically unsaturated monomer (a) is first added to an aqueous solvent, if necessary. The neutralizer is, for example, aqueous ammonia. Subsequently, the polymer emulsifier (B) is added to the aqueous solvent while heating the aqueous solvent as necessary. Subsequently, the polymerization initiator and the ethylenically unsaturated monomer (a) are added to the aqueous solvent while heating the aqueous solvent under an inert atmosphere. As a result, the ethylenically unsaturated monomer (a) is emulsion-polymerized in an aqueous solvent to synthesize the polymer particles (A). As a result, the aqueous polymer emulsion (X) is obtained. The reaction conditions for emulsion polymerization of the ethylenically unsaturated monomer (a) are appropriately set according to the composition of the polymer emulsifier (B), the composition of the ethylenically unsaturated monomer (a), and the like. ..
水性溶媒中にエチレン性不飽和単量体（ａ）を加える際には、あらかじめエチレン性不飽和単量体（ａ）を界面活性剤の存在下で乳化させることでプレ乳化物を作製してから、このプレ乳化物を溶媒に加えてもよい。この場合、ポリマー粒子が安定的に合成されやすく、かつエマルション粒子が安定して分散しやすい。また水性ポリマーエマルションから得られる膜が丈夫で、耐水性を有しやすい。 When the ethylenically unsaturated monomer (a) is added to an aqueous solvent, a pre-emulsified product is prepared by emulsifying the ethylenically unsaturated monomer (a) in the presence of a surfactant in advance. Therefore, this pre-emulsion may be added to the solvent. In this case, the polymer particles are likely to be stably synthesized, and the emulsion particles are likely to be stably dispersed. Further, the film obtained from the aqueous polymer emulsion is strong and easily has water resistance.
なお、水性ポリマーエマルション（Ｘ）を製造する方法は、上記のみには制限されない。 The method for producing the aqueous polymer emulsion (X) is not limited to the above.
メークアップ化粧料について説明する。メークアップ化粧料は、水性ポリマーエマルション（Ｘ）を含有する。そのため、メークアップ化粧料は、良好な凍結復元性を有しやすく、またメークアップ化粧料から作製された膜は良好なつやを有しやすい。 Makeup cosmetics will be described. The make-up cosmetic contains an aqueous polymer emulsion (X). Therefore, make-up cosmetics tend to have good freeze-restorability, and films made from make-up cosmetics tend to have good gloss.
メークアップ化粧料は、水性ポリマーエマルション（Ｘ）に加えて、適宜の添加剤を含有できる。例えばメークアップ化粧料は、可塑剤、皮膜形成剤、ゲル化剤、粉体、繊維、希釈剤、粘度調整剤、油剤、界面活性剤、紫外線吸収剤、褪色防止剤、酸化防止剤、消泡剤、保湿剤、香料、顔料、水性成分、無機酸、及び有機酸等からなる群から選択される少なくとも一種を含有できる。可塑剤は、例えばジプロピレングリコール、ジブチルフタレート、ジオクチルフタレート、クエン酸トリブチル、クエン酸アセチルトリブチル、及びカンフル等からなる群から選択される少なくとも一種を含有できる。特にメークアップ化粧料が可塑剤を含有すると、メークアップ化粧料から膜が特に作製されやすくなり、丈夫な膜を得られやすい。可塑剤の割合は、メークアップ化粧料に対して５質量％以下であることが好ましく、３質量％以下であることがさらに好ましい。この場合、エマルション粒子のＴｇが高く成膜性が低いメークアップ化粧料でも、べたつきを生じることなく、丈夫な膜が得られやすくなり、またこれにより膜のつやが更に良好になりやすい。 The make-up cosmetic may contain an appropriate additive in addition to the aqueous polymer emulsion (X). For example, make-up cosmetics include plasticizers, film-forming agents, gelling agents, powders, fibers, diluents, viscosity modifiers, oils, surfactants, UV absorbers, anti-fading agents, antioxidants, and defoamers. It can contain at least one selected from the group consisting of agents, moisturizers, fragrances, pigments, aqueous components, inorganic acids, organic acids and the like. The plasticizer can contain at least one selected from the group consisting of, for example, dipropylene glycol, dibutyl phthalate, dioctyl phthalate, tributyl citrate, acetyltributyl citrate, camphor and the like. In particular, when the make-up cosmetic contains a plasticizer, a film is particularly easily formed from the make-up cosmetic, and a strong film can be easily obtained. The proportion of the plasticizer is preferably 5% by mass or less, more preferably 3% by mass or less, based on the make-up cosmetics. In this case, even a make-up cosmetic having a high Tg of emulsion particles and a low film-forming property can easily obtain a strong film without causing stickiness, and thereby the gloss of the film tends to be further improved.
メークアップ化粧料は、上記の利点を有することから、特に爪用化粧料であることが好ましい。ただし、メークアップ化粧料は、爪用化粧料に限らず、アイライナー、マスカラ等であってもよい。 Since the make-up cosmetic has the above-mentioned advantages, it is particularly preferable to use a nail cosmetic. However, the make-up cosmetics are not limited to nail cosmetics, and may be eyeliner, mascara, or the like.
以下、本実施形態の具体的な実施例を提示する。なお、本実施形態は、以下の実施例のみには制限されない。 Hereinafter, specific examples of this embodiment will be presented. The present embodiment is not limited to the following examples.
１．水性ポリマーエマルションの調製
（１）実施例１〜２３、比較例１
高分子乳化剤として、表１〜３に示す組成を有する単量体（ｂ）の共重合体を用意した。表１〜３の単量体（ｂ）の成分の詳細は下記のとおりである。
Ａａ：アクリル酸（屈折率１．４２）。
ＭＡａ：メタクリル酸（屈折率１．４３）。
ＨＥＭＡ：メタクリル酸−２−ヒドロキシエチル（屈折率１．４５）。
ＭＭＡ：メタクリル酸メチル（屈折率１．４１）。
ＢＭＡ：メタクリル酸ブチル（屈折率１．４３）。
ＢＡ：アクリル酸ブチル（屈折率１．４１）。
ＨＡ：アクリル酸−２−エチルヘキシル（屈折率１．４４）。
ＬＭＡ：メタクリル酸ラウリル（屈折率１．４４）。
ｍＰＢＡ：ｍ−フェノキシベンジルアクリレート(屈折率１．５７）。
1. 1. Preparation of Aqueous Polymer Emulsion (1) Examples 1-23, Comparative Example 1
As a polymer emulsifier, a copolymer of the monomer (b) having the compositions shown in Tables 1 to 3 was prepared. Details of the components of the monomer (b) in Tables 1 to 3 are as follows.
Aa: Acrylic acid (refractive index 1.42).
MAa: Methacrylic acid (refractive index 1.43).
HEMA: -2-hydroxyethyl methacrylate (refractive index 1.45).
MMA: Methyl methacrylate (refractive index 1.41).
BMA: Butyl methacrylate (refractive index 1.43).
BA: Butyl acrylate (refractive index 1.41).
HA: -2-ethylhexyl acrylate (refractive index 1.44).
LMA: Lauryl methacrylate (refractive index 1.44).
mPBA: m-phenoxybenzyl acrylate (refractive index 1.57).
この高分子乳化剤のガラス転移温度（Ｔｇ）、酸価（ＡＶ）、及び重量平均分子量（Ｍｗ）は、表１〜３に示すとおりである。 The glass transition temperature (Tg), acid value (AV), and weight average molecular weight (Mw) of this polymer emulsifier are as shown in Tables 1 to 3.
また、ポリマー粒子を合成するためのモノマーとして、表１〜３に示す組成を有する単量体（ａ）を用意した。水５０質量部中で、単量体（ａ）１００質量部を、界面活性剤であるαオレフィンスルホン酸ナトリウムとジオクチルスルホコハク酸ナトリウムとの混合物１質量部の存在下で乳化することで、エチレン性不飽和単量体（ａ）のプレ乳化物を含む液を得た。表１〜３の単量体（ａ）の成分の詳細は下記のとおりである。
ＭＡａ：メタクリル酸（屈折率１．４２）。
ＨＥＭＡ：メタクリル酸−２−ヒドロキシエチル（屈折率１．４５）。
ＭＭＡ：メタクリル酸メチル（屈折率１．４１）。
ＢＭＡ：メタクリル酸ブチル（屈折率１．４３）。
ＢＡ：アクリル酸ブチル（屈折率１．４１）。
ＨＡ：アクリル酸−２−エチルヘキシル（屈折率１．４４）。
Ｓｔ：スチレン（屈折率１．５９）。
ＢＺＡ：ベンジルアクリレート（屈折率１．５１）。
ｍＰＢＡ：ｍ−フェノキシベンジルアクリレート（屈折率１．５７）。
ＨＰＰＡ：２−ヒドロキシ−３−フェノキシプロピルアクリレート（屈折率１．５３）。
Further, as a monomer for synthesizing polymer particles, a monomer (a) having the compositions shown in Tables 1 to 3 was prepared. In 50 parts by mass of water, 100 parts by mass of the monomer (a) is emulsified in the presence of 1 part by mass of a mixture of sodium α-olefin sulfonate and sodium dioctyl sulfosuccinate as a surfactant to make it ethylenically. A liquid containing a pre-emulsion of the unsaturated monomer (a) was obtained. Details of the components of the monomer (a) in Tables 1 to 3 are as follows.
MAa: Methacrylic acid (refractive index 1.42).
HEMA: -2-hydroxyethyl methacrylate (refractive index 1.45).
MMA: Methyl methacrylate (refractive index 1.41).
BMA: Butyl methacrylate (refractive index 1.43).
BA: Butyl acrylate (refractive index 1.41).
HA: -2-ethylhexyl acrylate (refractive index 1.44).
St: Styrene (refractive index 1.59).
BZA: Benzyl acrylate (refractive index 1.51).
mPBA: m-phenoxybenzyl acrylate (refractive index 1.57).
HPPA: 2-hydroxy-3-phenoxypropyl acrylate (refractive index 1.53).
反応容器として、還流冷却器、温度計、窒素吹込管、滴下漏斗、及び攪拌機が取り付けられた容量１リットルの４つ口フラスコを用い、この反応容器中に溶媒である水９０質量部と２５％アンモニア水とを加えた。２５％アンモニア水の量は、高分子乳化剤中のカルボキシル基の中和率が１００％になるように調整した。 As the reaction vessel, a four-necked flask with a capacity of 1 liter equipped with a reflux condenser, a thermometer, a nitrogen blowing tube, a dropping funnel, and a stirrer was used, and 90 parts by mass of water as a solvent and 25% were contained in the reaction vessel. Ammonia water was added. The amount of 25% aqueous ammonia was adjusted so that the neutralization rate of the carboxyl group in the polymer emulsifier was 100%.
反応容器内に高分子乳化剤を徐々に加え、反応容器内の液を７０℃まで昇温して１時間保持することで高分子乳化剤を液中に溶解させた。続いて反応容器内の液を窒素気流下で８０℃まで昇温した。続いて反応容器内にプレ乳化物を含む液と、開始剤である過硫酸アンモニウム（ＡＰＳ）の５％水溶液とを、一緒に、４時間かけて滴下した。各成分の配合量は表１〜３の「配合量」の欄に示すとおりである。これにより、反応用器内に、水性ポリマーエマルションを得た。 The polymer emulsifier was gradually added to the reaction vessel, and the solution in the reaction vessel was heated to 70 ° C. and held for 1 hour to dissolve the polymer emulsifier in the solution. Subsequently, the temperature of the liquid in the reaction vessel was raised to 80 ° C. under a nitrogen stream. Subsequently, a liquid containing the pre-emulsion and a 5% aqueous solution of ammonium persulfate (APS) as an initiator were added dropwise to the reaction vessel together over 4 hours. The blending amount of each component is as shown in the “blending amount” column of Tables 1 to 3. As a result, an aqueous polymer emulsion was obtained in the reaction vessel.
（２）比較例２、３
ポリマー粒子を合成するためのモノマーとして、表３に示す組成を有する単量体（ａ）を用意した。水５０質量部中で、単量体（ａ）１００質量部を、界面活性剤であるαオレフィンスルホン酸ナトリウムとジオクチルスルホコハク酸ナトリウムとの混合物１質量部の存在下で乳化することで、エチレン性不飽和単量体（ａ）のプレ乳化物を含む液を得た。
(2) Comparative Examples 2, 3
As the monomer for synthesizing the polymer particles, the monomer (a) having the composition shown in Table 3 was prepared. In 50 parts by mass of water, 100 parts by mass of the monomer (a) is emulsified in the presence of 1 part by mass of a mixture of sodium α-olefin sulfonate and sodium dioctyl sulfosuccinate, which are surfactants, to form an ethylenic property. A liquid containing a pre-emulsion of the unsaturated monomer (a) was obtained.
反応容器として、還流冷却器、温度計、窒素吹込管、滴下漏斗、及び攪拌機が取り付けられた容量１リットルの４つ口フラスコを用い、この反応容器中に溶媒である水９０質量部と、界面活性剤としてαオレフィンスルホン酸ナトリウムとジオクチルスルホコハク酸ナトリウムとの混合物を加え、続いて反応容器内の液を窒素気流下で８０℃まで昇温した。続いて反応容器内にプレ乳化物を含む液と、開始剤である過硫酸アンモニウム（ＡＰＳ）の５％水溶液とを、一緒に、４時間かけて滴下した。各成分の配合量は表３の「配合量」の欄に示すとおりである。これにより、反応用器内に、水性ポリマーエマルションを得た。 As the reaction vessel, a four-necked flask with a capacity of 1 liter equipped with a reflux condenser, a thermometer, a nitrogen blow tube, a dropping funnel, and a stirrer was used, and 90 parts by mass of water as a solvent and an interface with the reaction vessel were used. A mixture of sodium α-olefin sulfonate and sodium dioctyl sulfosuccinate was added as an activator, and then the liquid in the reaction vessel was heated to 80 ° C. under a nitrogen stream. Subsequently, a liquid containing the pre-emulsion and a 5% aqueous solution of ammonium persulfate (APS) as an initiator were added dropwise to the reaction vessel together over 4 hours. The blending amount of each component is as shown in the “blending amount” column of Table 3. As a result, an aqueous polymer emulsion was obtained in the reaction vessel.
２．評価試験
下記の評価試験を行った。その結果を表１〜３に示す。
2. Evaluation test The following evaluation test was conducted. The results are shown in Tables 1 to 3.
（１）ポリマー粒子のガラス転移温度（Ｔｇ）
ポリマー粒子のガラス転移温度（Ｔｇ）は、単量体（ａ）の組成割合から理論的に計算される値であり、下記のＦｏｘの式で算出した値である。
１／Ｔｇ＝Ｗ１／Ｔｇ１＋Ｗ２／Ｔｇ２＋・・・＋Ｗｎ／Ｔｇｎ
上記Ｆｏｘの式において、ｎは１以上の整数であり、単量体（ａ）として用いるモノマーの種類を示す。すなわち、ｎ種類のモノマーの重合によってポリマー粒子を得た場合の計算式である。Ｗ１，Ｗ２，・・・Ｗｎは、ｎ種類のモノマーの各質量分率を示し、Ｔｇ１，Ｔｇ２，・・・Ｔｇｎは、ｎ種類のモノマーのホモポリマーの各ガラス転移温度を示す。上記Ｆｏｘの式におけるガラス転移温度の単位は絶対温度「Ｋ」であり、その計算値をセルシウス温度「℃」に変換した値をポリマー粒子のガラス転移温度とする。
(1) Glass transition temperature (Tg) of polymer particles
The glass transition temperature (Tg) of the polymer particles is a value theoretically calculated from the composition ratio of the monomer (a), and is a value calculated by the following Fox formula.
1 / Tg = W 1 / Tg 1 + W 2 / Tg 2 + ... + W n / Tg n
In the above Fox formula, n is an integer of 1 or more, and indicates the type of monomer used as the monomer (a). That is, it is a calculation formula when polymer particles are obtained by polymerization of n kinds of monomers. W 1 , W 2 , ... W n indicate each mass fraction of n kinds of monomers, and Tg 1 , Tg 2 , ... Tg n are the glass transition temperatures of homopolymers of n kinds of monomers. Is shown. The unit of the glass transition temperature in the Fox equation is the absolute temperature “K”, and the value obtained by converting the calculated value into the Celsius temperature “° C.” is defined as the glass transition temperature of the polymer particles.
（２）エマルション粒子のガラス転移温度（Ｔｇ）
エマルション粒子のガラス転移温度（Ｔｇ）を、示差走査熱量計（ＤＳＣ）により測定した。
(2) Glass transition temperature (Tg) of emulsion particles
The glass transition temperature (Tg) of the emulsion particles was measured by a differential scanning calorimetry (DSC).
（３）エマルション安定性
水性ポリマーエマルションを４０℃雰囲気下に３０日間暴露し、その間に沈降物が認められない場合を「Ａ」、沈降物がわずかに見られる場合を「Ｂ」と、評価した。
(3) Emulsion stability The aqueous polymer emulsion was exposed to an atmosphere of 40 ° C. for 30 days, and the case where no sediment was observed during that period was evaluated as "A", and the case where a slight amount of sediment was observed was evaluated as "B". ..
（４）凍結復元性
水性ポリマーエマルション２０ｇを、−２０℃の雰囲気下に２時間曝露することで、凍結させた。続いて水性ポリマーエマルションを室温で解凍した。解凍後の水性ポリマーエマルションを観察し、流動性が損なわれておらず、かつ沈降物が認められない場合は「Ａ」、流動性が損なわれていないが沈降物が認められた場合は「Ｂ」、流動性が損なわれ、かつ沈降物が認められる場合は「Ｃ」と、評価した。
(4) Freezing Restorability 20 g of the aqueous polymer emulsion was frozen by exposing it to an atmosphere of −20 ° C. for 2 hours. The aqueous polymer emulsion was then thawed at room temperature. Observe the aqueous polymer emulsion after thawing, and if the fluidity is not impaired and no sediment is observed, "A", and if the fluidity is not impaired but sediment is observed, "B". , When the fluidity was impaired and sediment was observed, it was evaluated as "C".
（５）膜評価
試料として実施例１〜５、８〜１１、１４〜２３及び比較例１〜３の場合は水性ポリマーエマルションをそのまま用い、実施例６、７、１２、１３の場合は水性ポリマーエマルションに可塑剤としてジプロピレングリコールを表１、２に示す含有割合になるように加えたものを用いた。
(5) Membrane Evaluation As samples, the aqueous polymer emulsion was used as it was in the cases of Examples 1 to 5, 8 to 11, 14 to 23 and Comparative Examples 1 to 3, and in the cases of Examples 6, 7, 12, and 13, the aqueous polymer was used. An emulsion in which dipropylene glycol was added as a plasticizer so as to have the content ratios shown in Tables 1 and 2 was used.
ネイル用の刷毛を用いて、ガラス板に試料を塗布してから、自然乾燥させることで、膜を作製した。 A film was prepared by applying a sample to a glass plate using a nail brush and then allowing it to air dry.
（５−１）成膜性
膜を観察した結果に基づいて成膜性を評価した。評価にあたっては、膜にクラックが入っていない場合を「Ａ」、膜にわずかにクラックが入っている場合を「Ｂ」、膜に大きなクラックが入り、または多数のクラックが入っている場合を「Ｃ」と、評価した。
(5-1) Film forming property The film forming property was evaluated based on the result of observing the film. In the evaluation, "A" is when the film is not cracked, "B" is when the film is slightly cracked, and "B" is when the film is large cracked or has many cracks. It was evaluated as "C".
（５−２）耐水性
膜を４０℃の水に１０分浸漬してから、膜の外観を観察した。その結果、膜に変色及び白濁が認められない場合を「Ａ」、膜がやや青白くなった場合を「Ｂ」、膜が白濁した場合を「Ｃ」と、評価した。
(5-2) The water resistant membrane was immersed in water at 40 ° C. for 10 minutes, and then the appearance of the membrane was observed. As a result, the case where no discoloration or cloudiness was observed in the film was evaluated as "A", the case where the film became slightly pale was evaluated as "B", and the case where the film became cloudy was evaluated as "C".
（５−３）つや
１０人の評価者が、膜の外観を観察して、膜のつやの程度を判断した。その結果、つやが良好であると判断した評価者が７人以上である場合を「Ａ」、３人以上６人以下である場合を「Ｂ」、２人以下である場合を「Ｃ」と、評価した。
(5-3) Gloss 10 evaluators observed the appearance of the film and judged the degree of gloss of the film. As a result, the case where the number of evaluators judged to have good gloss is 7 or more is "A", the case where the number is 3 or more and 6 or less is "B", and the case where the number is 2 or less is "C". ,evaluated.
（５−４）べたつき
１０人の評価者が、膜を指で触れ、膜のべたつきの程度を判断した。その結果、べたつくと判断した評価者が２人以下である場合を「Ａ」、３人以上５人以下である場合を「Ｂ」、６人以上である場合を「Ｃ」と、評価した。
(5-4) Stickiness Ten evaluators touched the membrane with their fingers to judge the degree of stickiness of the membrane. As a result, the case where the number of evaluators judged to be sticky was 2 or less was evaluated as "A", the case where the number was 3 or more and 5 or less was evaluated as "B", and the case where the number was 6 or more was evaluated as "C".
Claims (13)
前記ポリマー粒子（Ａ）は、エチレン性不飽和単量体（ａ）の重合体であり、
前記高分子乳化剤（Ｂ）は、エチレン性不飽和単量体（ｂ）の重合体であり、
前記エチレン性不飽和単量体（ａ）と前記エチレン性不飽和単量体（ｂ）とのうち少なくとも一方は、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有する、
水性ポリマーエマルション。 Contains polymer particles (A), polymer emulsifier (B), and water (C),
The polymer particles (A) are polymers of the ethylenically unsaturated monomer (a).
The polymer emulsifier (B) is a polymer of an ethylenically unsaturated monomer (b).
At least one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. ,
Aqueous polymer emulsion.
請求項１に記載の水性ポリマーエマルション。 The ethylenically unsaturated monomer (a) contains the ethylenically unsaturated monomer (c), and the ethylenically unsaturated monomer (a) is relative to the ethylenically unsaturated monomer (a). ), The proportion of the ethylenically unsaturated monomer (c) is 1% by mass or more and 80% by mass or less.
The aqueous polymer emulsion according to claim 1.
請求項１又は２に記載の水性ポリマーエマルション。 The ethylenically unsaturated monomer (b) contains the ethylenically unsaturated monomer (c), and the ethylenically unsaturated monomer (b) is relative to the ethylenically unsaturated monomer (b). ), The proportion of the ethylenically unsaturated monomer (c) is 1% by mass or more and 80% by mass or less.
The aqueous polymer emulsion according to claim 1 or 2.
請求項１から３のいずれか一項に記載の水性ポリマーエマルション。 The ethylenically unsaturated monomer (c) contains at least one of m-phenoxybenzyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate.
The aqueous polymer emulsion according to any one of claims 1 to 3.
請求項１から４のいずれか一項に記載の水性ポリマーエマルション。 The ratio of the polymer emulsifier (B) to the ethylenically unsaturated monomer (a) is 15% by mass or more and 60% by mass or less.
The aqueous polymer emulsion according to any one of claims 1 to 4.
請求項１から５のいずれか一項に記載の水性ポリマーエマルション。 The glass transition temperature of the polymer particles (A) is 10 ° C. or higher and 60 ° C. or lower.
The aqueous polymer emulsion according to any one of claims 1 to 5.
請求項１から６のいずれか一項に記載の水性ポリマーエマルション。 The acid value of the polymer emulsifier (B) is 70 mgKOH / g or more and 250 mgKOH / g or less.
The aqueous polymer emulsion according to any one of claims 1 to 6.
請求項１から７のいずれか一項に記載の水性ポリマーエマルション。 The ethylenically unsaturated monomer (b) contains a (meth) acrylic acid ester (b2) having an alkyl group having 8 or more and 18 or less carbon atoms.
The aqueous polymer emulsion according to any one of claims 1 to 7.
請求項８に記載の水性ポリマーエマルション。 The ratio of the (meth) acrylic acid ester (b2) is 5% by mass or more and 60% by mass or less with respect to the ethylenically unsaturated monomer (b).
The aqueous polymer emulsion according to claim 8.
請求項１から９のいずれか一項に記載の水性ポリマーエマルション。 For make-up cosmetics,
The aqueous polymer emulsion according to any one of claims 1 to 9.
メークアップ化粧料。 The aqueous polymer emulsion according to claim 10 is contained.
Makeup cosmetics.
請求項１１に記載のメークアップ化粧料。 Nail cosmetics,
The make-up cosmetic according to claim 11.
水性溶媒中で前記高分子乳化剤（Ｂ）の存在下でエチレン性不飽和単量体（ａ）を乳化重合することで前記ポリマー粒子（Ａ）を合成することを含み、
前記高分子乳化剤（Ｂ）は、エチレン性不飽和単量体（ｂ）の重合体であり、
前記エチレン性不飽和単量体（ａ）と前記エチレン性不飽和単量体（ｂ）とのうち少なくとも一方は、屈折率１．５０以上のエチレン性不飽和単量体（ｃ）を含有する、
水性ポリマーエマルションの製造方法。 A method for producing an aqueous polymer emulsion containing polymer particles (A), a polymer emulsifier (B), and water (C).
It comprises synthesizing the polymer particles (A) by emulsion polymerization of the ethylenically unsaturated monomer (a) in the presence of the polymer emulsifier (B) in an aqueous solvent.
The polymer emulsifier (B) is a polymer of an ethylenically unsaturated monomer (b).
At least one of the ethylenically unsaturated monomer (a) and the ethylenically unsaturated monomer (b) contains an ethylenically unsaturated monomer (c) having a refractive index of 1.50 or more. ,
A method for producing an aqueous polymer emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020064323A JP2021161066A (en) | 2020-03-31 | 2020-03-31 | Aqueous polymer emulsion, makeup cosmetic, and method for producing aqueous polymer emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2020064323A JP2021161066A (en) | 2020-03-31 | 2020-03-31 | Aqueous polymer emulsion, makeup cosmetic, and method for producing aqueous polymer emulsion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2021161066A true JP2021161066A (en) | 2021-10-11 |
Family
ID=78004325
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2020064323A Pending JP2021161066A (en) | 2020-03-31 | 2020-03-31 | Aqueous polymer emulsion, makeup cosmetic, and method for producing aqueous polymer emulsion |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2021161066A (en) |
-
2020
- 2020-03-31 JP JP2020064323A patent/JP2021161066A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4792052B2 (en) | Aqueous copolymer dispersion and coating composition | |
| JP6761282B2 (en) | Phosphoric acid functionalized coating composition | |
| EP1682586A2 (en) | Aqueous dispersions containing multi-stage emulsion polymers | |
| JP2010261050A (en) | Aqueous polymer dispersion | |
| BR112013021237A2 (en) | process and composition | |
| JP2006225656A (en) | Thickening agent for aqueous system | |
| CN112969729A (en) | Multistage polymers | |
| JPH03133916A (en) | Water-based manicure | |
| TW548282B (en) | Emulsion polymers | |
| JP3776226B2 (en) | Water-based beauty nail | |
| JP2005281339A (en) | Resin particle dispersion, method for producing the same and application thereof | |
| JP2021161066A (en) | Aqueous polymer emulsion, makeup cosmetic, and method for producing aqueous polymer emulsion | |
| FR2803743A1 (en) | COSMETIC COMPOSITIONS CONTAINING AQUEOUS DISPERSIONS OF POLYMERS, FILMOGENS IN THE ABSENCE OF ORGANIC SOLVENT | |
| JP2013129738A (en) | Emulsion for vibration damping material, method for producing the same, and coating material composition | |
| JP2002255748A (en) | Method for producing nonaqueous liquid dispersion | |
| JP6981963B2 (en) | Gel composition, cosmetics, and method for producing gel composition | |
| LU101910B1 (en) | Polymer emulsions containing a ploymerized surfactant and methods for production and use thereof | |
| JP7146160B1 (en) | Aqueous resin composition and method for producing coated article | |
| JP5154815B2 (en) | Solvent-based nail polish | |
| WO2024090354A1 (en) | Aqueous polymer emulsion for cosmetic, method for producing same, and cosmetic | |
| JPH04297409A (en) | Water-based manicure | |
| JPH05255041A (en) | Film-forming cosmetic | |
| JP6419255B1 (en) | Aqueous resin dispersion for cosmetics, method for producing the same, and cosmetics | |
| JP2005015697A (en) | Method for producing aqueous emulsion composition | |
| JPH04297408A (en) | Water-based manicure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20230327 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20240402 |